CA2145666A1 - Support catalyst and use of same - Google Patents
Support catalyst and use of sameInfo
- Publication number
- CA2145666A1 CA2145666A1 CA002145666A CA2145666A CA2145666A1 CA 2145666 A1 CA2145666 A1 CA 2145666A1 CA 002145666 A CA002145666 A CA 002145666A CA 2145666 A CA2145666 A CA 2145666A CA 2145666 A1 CA2145666 A1 CA 2145666A1
- Authority
- CA
- Canada
- Prior art keywords
- supported catalyst
- catalyst according
- reaction
- weight
- pore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F1/00—Designs or pictures characterised by special or unusual light effects
- B44F1/02—Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces
- B44F1/04—Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces after passage through surface layers, e.g. pictures with mirrors on the back
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention concerns a supported catalyst in the form of packing and constructed on an open-pore support material on whose external and internal surfaces a macro-porous ion exchange resin is mechanically and/or chemically affixed.
Description
` 21~66~
I SUB~ u~ PAGE
. $'l1'L~'Led catalyst and use of sx~e The inven~ion co~rnc a ~nppo~ted catalyst and use of sa~e.
The development o~ new supported catalyst ~on~ n~ sulphonic a~id y~ ~u~s on a polymer frame, is of great impor~ance for a numker of in~u~LLial ch~mical pro~esses, for example the p~oduction of certain ethers from the reaction of c~ or c~
fractions of the refine~y technology with met~hAnnl or e~h~n~l as admix co~ponents for the production o~ f~el (~f. ~y~vcarbon Processing, Nove~ber l990, pp.12~, 128).
To produ~e i~ved, par~icularly more environme~ally f~iendly an~ no~k pet~ol qu~lities, me~hyl tertia~y butylene ether (NTBE) and tertiary amyl ~e~hyl ether (TAME) or tertiary butylene ethylether (ETBE) are particularly i~poLk~lL a~m;Y
componen~s.
The procrcc~s to p~oduce these components a~e generally car~ied o~t as ~eaction distilla~ion processes or processes to t~ea~
and/or re~ct t~e ~ G~ S ~y cataly~ic distillation.
In case o~ catalytic distillation the reaction and ~he processing of the reaction mixture by distill~ion andfo~
rectific~tion, ~hich ~ y tak~s place in a following step of the process, are ca~ried ~u~ in one single rea~ion appa~atus only, which also incl~des the processing part.
In this c~ction ~he illLL~uc~ion ~nd affixing of ~e catalys~ in the reaF~ion apparat~s represe~ a special problem. Usually in ~he ~ase o~ solid or supported catalysts a fil~ing o~ the catalys~ into one or several superposed solid keds, ~er~A=ted by the re~ction ~ixtu~e, is provided.
When the ~acro-porous cross-linkeq polystyrene sulphoni~ acid, used in the industrial proauct70n of the MTBE or TA~E, is used in spherical form as loose filling m a s017d bed as cat~lyst in the reaction of meth~nol and buty~ene, disadv~n~ages like 214~6~ 6 S~B~ ul~ PAGE
h;gher resista~ce to flow, edge flow as well as fhe wear of ~he catalyst are invol~ed.
To a~oid ~hese disadvantages in a process to ca ~ ou~ c~emica~
reactions in a ~eaction-distillation appa~atus ~t has been ~ro~osed to ~cco~odate the ca~alyst consisfing of macro-porous cross-linked gel p4llets of a polys~y~le sulphonic acid Ln closed pouc~es, which ~e constru~ted from and retained by a wi~e netting and are assigned to a solid ked made to suit ~he ~eac~ion apparatus ~y coilin~ in t~e form of a spiral, c~.
EP-A-O 4~6 954.
It has been further p~u~osed ~or the p~rpose of i p~oving the ma~erial ~ch~n~e ~ro~e~ ~ies of the solid bed catalyst p~r,~;~g ~o cons~ruct t~e catalyst in the shape of e~ n~e bodies like R~schig rings, fo~ which purpose a mixture of cross-l;nk~A
~ty~,e divinyl ben2ene eop~lymer in y~o~l~ form is coex~ruded with the thermoplastic poly~ro~ylene to such an PYch~nge s~ape and is s41phonated a~terwards, cf. FR-A-2 297 083.
~0 This co~pt has been fu~ther developed inasmuch the formed bodies were ~Lodu~ed direc~ly from macro-porous ion ~oh~n~e resins without the ~se of a the~moplastic ~aterial, ~f. DE-A-3 930 515. ~he formed bodies ob~ine~ by this me~hod ha~e ~he expected g~od ~aterial ~Yc~ge prope~ties as well as a good catalytic activity. It is, howe~er, not easy to-~anufacbure these in pro~t;~n quantities and t~ey leave a lo~ to be desired ~ega~ding ~heir nech~n;cal ~LLengLh.
33 From US 4 ~50 052 supported ~a~alyst~ are known 7n ~he form of a pac~ing, whic~ can be coated with a poly~er made of vin~l aromati~ mononers and can be su~seguently sulphonated. For this ~ul~se the poly~er is dissolved, applied to the s~pport an~
~he solvent is ~hen ~emoved again. A ~is2d~antage of this process and/or of the catalyst prP~09~ in ~his ~anner is that the polymers men~ioned cannot be stron~ly c~oss-lin~e~ as otherwise they could no~ be ~iscQl~e~. The result o~ ~his is that ~hey can be corroded, separated or dissolved by the 21~5fi~i~
S~BSl~ U'l'~` 3?AGE
reacticn ~ixture also. ~n addition, in the r~nne~ ~entioned, no macro-po~osity for t~e poly~er can be achieved.
The ob~ec~ of the in~en~on is to produce a ~ uL~ed catalyst $ with ~ater7al ~Y~-hRnge p~operties which can be also ~Lo~ ce~ in prod~ion qu2ntities.
Th~s ob~ective is ac~ieved by suppo-ted catalysts accord;ng to the cl~im~ 1 to 14 as well ~s ~y a process to carry ou~
c~emical reactions by using these supported ~atalysts according to claLms 15 to 24.
The ~u~o~ed c~talysts according to t~e invention in t~e form of p~ckin~ are cohstructed from a basic body ~o~C~ting of open poro~s ~u~o~L ma~erial, on the external and intern~l sur~ace of which a macro-porous ion e~-h~n~e resin is affixed me~han~cally and/or chemically.
A che~ical affixing ma~ be preferred and is obt~ined, ~or example ~y sil~ ing the surface o~ the open-po~ous ~u~o~
~atexial with su~sequent polymerisation ~uild-up.
The packing of the supporte~ ~atalyst is constructed as R~ ;g rings, Berl s~adles, ~orus saddles, packing rings W7t~ web o~
cross web, Pall rings, o~her hollow bod~es, hollow sphe~es, ordered packages, ho~eycom~ bodies and the like~with a proportion o~ the hollow space o~ ~he ma~ro ~OL~uS ~on e~ n~e resin ~eLng 5 to g5 ~.
The SUp~vr L material o~ the aforementioned ~p~uLLed ~atalys~
consists of open-pore glass, sinte~ed gl~ss, open-pore ceramic material on al~minium silioate ~ase, sintered glass ceramics, foam ~eramics, ac~iva ed c~rh~n or activa~ed coke.
In the case of sintered glass o~ sintered glass cerami~s ~he surface area can be increased by a prio~ treatme~t with aqueous alk~i hyd~uxide solution. By this the nllmh~r of silanol groups on the surface will ke incre~sed o~ the one hand, wh~h surface 21~366~
i S~B~ ul~ PAGE
is ~hen accessi~le for ~ n;s~tion and by ~he etching process a rougher surface is cre~ed on the othe~, thereby favouring a me~h~n;cal af f i~; ng on the polymer applied.
While glass with open pores, sintered glass, sintered glass ics or cera~ic ~terial with open pores are c~mr~rcial~y a~ e al~eady ~n a basic or p~ckin~ form suit241e for material e~ch~nge ~uuposes, activ~ed c~r~on or ac~ivated coke . with suitable pore sizes can be use~ according to the in~en~ion 1~ for cat~lyst beds. Suitable po~e sizes are obtained f~om bulk material a~ter a selection process ~rom sui~able sieved - material in selected size ranges~
T~e macro-poro~s ion ~Y~ nge resin on and in the ~u~o~
~aterial is preferably a macro-porous cross-linked poly~yre~.e sulp~onic acid, where~y a diferen~ degree o~ cro~s-l;nk;ng can be accomplished to correspond wit~ the requLrements by using greater or lesser a~ounts of di~nyl be~zene or diisopropenyl benzene. ~he polymer is preferably cross-linked to such a high degree, ~hat it cannot be disso~ed by ~he rea~tion mixture of the reaction to be c~taly~ed.
The ion ~Y~h~nge ~esin can be appl~ed to the suppart material by two different proc~s~.
~n case of ~he so called i~prey~.ating polyme~isIng ~ ess the for~ed ho~7es are i~ yrlated with the rea~tion mixture, the ~ s~ imp~egna~ing solution is removed ~nd subsequently ~he poly~erisation is carried out.
In ~ase of ~he precipitating poly~erising proce~s the pa~ing is in ~ in the reaction mixture during the polyme~isation.
The ad~antages of the pre~ipitation polymerising process are a very uniform dis~ribution o~ the polymer Ln the pores of the support ~aterial, in ~ddi~70n a high porosity, since the sol~ent can act ~s a pore former, as ~ell as the sLmple pxoduction man~er, since no steps are required to even out ~he distribution of ~he mono~ers on the support.
214~6~
~BS~ ul~ PAGE
An addi~ion~l ad~antage is that the polymRr content in the comple~ed ion e~h~ resin can be set simply by ~he ratio of a suitable solven~ to ~he nono~er mixture and that ~he polymer, when using the appLu~.ia~e solven~, is already in the swollen form so that po~ dam2ge of the ~ L ma~erial by the sw~ g process can be avoided to ~ great exten~. Ne~h~nol or ~-oct~ne, as ~ell as pent~de~Ane may ~e used as solvents. A
C~- to ~l7-n-paraf~in fraction can also be used.
i~ By the pro~ess ~entioned ~ ma~r O POL~US poly~er is pro~r~e~ in t~e pores and on the surface of porous p~cking, which will su~sequen~ly receive ion ~c~nge properties by su~phonation.
In case of the precipi~ating polymerisation process the poly~erisation is carried out depending on the ~o~n~aLion of ~he original materials sLy~.e and divinyl benzene or disopropyl benzene in the pore former or o~ ~he sol~ent in the pores of the packing up to ~hat degree of polymerisation, ~t which the formed poly~er in fla~y form beco~ insoluble in the pore for~er and/or the solvent and precipitates. The polymer fl~kes produced in this manner in ~e pores of the ~up~uLL
m~ter~al can be affixed in the pores of the suppo~t material purely ~h~n;C~lly and zre pro~ected from mechanical damages by the surrolm~in~ ~u~o~ mat~ri~l.
For cert~in rea¢tions it is useful to ~reat supported catalysts of ~he type described abo~e with G~oup7 or Group 8 metals of the periodic ta~le, particula~ly with p~ ium, platinum, ruthenium or rhodium ~n q~antities of 0.1 ~o 100 g/~g of ~he ion e~ nge res~n.
As has alrea~y ~een ;nfli~ted, ~he polymer can be addit~onally a~fixed che~ically on the $Upport material. A suitab~e ~hemical coupler is used ~o~ this purpose. ~or example sil2nes are sui~a~le co~plers for all formed hodies whi~h have OH gL~uys on their sur~a~es.
- 214~6~
I S~B~ Ul~ PAGE
If ~he polymer to be coupled has a Yinyl~c monomer base, ~inyl-group ~ ~ ing s;l~nes are prefer~ed as couplers, par~;Y
phenyl-7Jinyl diethoxysilane, phenyl-methyl vinyl silane, ~riethoxy-~inyl ~ nP or trichlor-~inyl silane.
~he supporte~ catalyst can be pro~eA by impregnating the pa~king with 0.1 to ~0% by weight with a mixture cnn~is~ing of 10 to 80, preferab7.y 30 to 70% by weight o~ S~yl~-e, ~ to 25, preferably 5 to 10~ by ~eight of di~inyl h~n~sne~ 1 to 8~, prefera~ly 20 to S0~ ~y weight of a pore forme~ or of a sol~en~
as wel~ as an effective quantity of a polymerisation in7tiator.
carryi~g out the polymerisation reaction under a te~peratuXe _ncre2se of 30- to 90~; and subsequently tre2ting ~he polymer material affixed in the pores of the pack~ng with a sulphonating 2cid. In this case the proportion ~y weight of t~e pore former or of ~he solvent is selected so that the proportion by weight of the ~ixture of ~y~-ene and di~inyl benzene adds up to 100~ by weigh~.
A supported ~talys~ pro~tlce~ according ~o ~he precipi~ating polymerisation process can be obt~;n~ by adding a mixture of 10 to 80, pre~erably 20 t~ 50% by ~eight o~ s~yrene, 2 to 2~, p~eferably ~ to 10~ ~y weight of di~i~yl behzene, 1 t~ 88, preferably 20 to 50% ~y weig~ of a pore former or solvent as well ~s 2n ef~ective quantity of a polyme~isati~n ini~iator on the one hand and a ~- to ~l7-n-par~ffin fraction on the other in a weight ra~io of 10 to 1 to 1 to 10, to 5 to 50~ by wei~h~
of the suppo~t material, b~sed on the total mixture~
~onditioning it under ~acuum, polymerising, was~ m g out the e~c~ pore former and ex~ern~lly adheri~g polymex gel, followed by sulphona~ing.
As po~e for~ers ~6- to ~ alkanes, e.g. n-~eptane, pentadecane, i-octane ~s well as Cg~ to C~-fractions of the n-paraffin production ~n ~e used. These pore forme~s ha~e good solubility for the ~y~e and divinyl ~enzene ~onomers used for the produ~ion of t~e ion exchange ~esin, but only 2 sligh~
- 2i4~66~
S~B~ ul~ ~A~E
sw~llin~ ability for the polymer produced tcf. Catalytic ~hemistry, Bruce C~ Gates, John Wiley & Sons, lg92, p.221).
In th~s manner a solid phase, con~isting pre~erably Of 5 m~L.,.~.h~es, is formed in ~e hollow spaces of ~e ~u~o~ and on the support material, and the volume ori~inal~y o~ r;ed by the sol~ent for t~e mono~ers remalns as ~acro-pores after the remo~al of ~he solvent, which pass th~ough the entire cross-linked polysty~ene and thus enable a good ~ of the reacting ~aterials fo~ the intpn~ chemical reactions after sulp~ona~ion. At the same ti~ne arl increase of ~he active sur~ac:e can ~e achieved by this.
Thi~ is why in a pre~e~red ~ho~;~ent the pore ~ormers can ke also solvents for the m~nomer mixture in case o~ the pre~ipitation polymerisation. ~n case of the precipitation polymerisation lower ~lkAnol$ like methanol are also suita~le as sol~ent. Combina~ions of solYent and pore former can also be used~
~0 The sulphonating a~id may be an ~ro~ati~ or an ~ h~t~c sulp~ir, acid, chlorosnlrhn~ic acid or s~lph~ric acid.
Furthe~ e, sl~ ur dioxide as well as sulphur dioxide addi~ion c~o~ ds like tha~ of dioxane, dime~hyl ~ l;ne or ~5 pyri~iine are suiWle.
S~lrht$ric acid is less prefera~le, as t~e ~ ,~dtion n~c~s~ry for ~deglla~e sulphonation has a notice~hl~ o~ C;rl~
a~fe~ ~nd may lead ~o ~he disinteyLa~ion of the polymer fra~e.
.
Prefer~ed aro~a~ic sulphonic acids are ~enzene sulphonic acids an~ p~efer~ed ~liEJhatic sulph~ acids ~e me~yl sulphonic ~c~ids ~
35 In a fu~ther preferred e~odiment ~he aci~s ~na~ also con~ain sol~ents like ch3 oro~o~, ni~rome~hane or ac:etonitrile~
I SUB~ u~ PAGE
. $'l1'L~'Led catalyst and use of sx~e The inven~ion co~rnc a ~nppo~ted catalyst and use of sa~e.
The development o~ new supported catalyst ~on~ n~ sulphonic a~id y~ ~u~s on a polymer frame, is of great impor~ance for a numker of in~u~LLial ch~mical pro~esses, for example the p~oduction of certain ethers from the reaction of c~ or c~
fractions of the refine~y technology with met~hAnnl or e~h~n~l as admix co~ponents for the production o~ f~el (~f. ~y~vcarbon Processing, Nove~ber l990, pp.12~, 128).
To produ~e i~ved, par~icularly more environme~ally f~iendly an~ no~k pet~ol qu~lities, me~hyl tertia~y butylene ether (NTBE) and tertiary amyl ~e~hyl ether (TAME) or tertiary butylene ethylether (ETBE) are particularly i~poLk~lL a~m;Y
componen~s.
The procrcc~s to p~oduce these components a~e generally car~ied o~t as ~eaction distilla~ion processes or processes to t~ea~
and/or re~ct t~e ~ G~ S ~y cataly~ic distillation.
In case o~ catalytic distillation the reaction and ~he processing of the reaction mixture by distill~ion andfo~
rectific~tion, ~hich ~ y tak~s place in a following step of the process, are ca~ried ~u~ in one single rea~ion appa~atus only, which also incl~des the processing part.
In this c~ction ~he illLL~uc~ion ~nd affixing of ~e catalys~ in the reaF~ion apparat~s represe~ a special problem. Usually in ~he ~ase o~ solid or supported catalysts a fil~ing o~ the catalys~ into one or several superposed solid keds, ~er~A=ted by the re~ction ~ixtu~e, is provided.
When the ~acro-porous cross-linkeq polystyrene sulphoni~ acid, used in the industrial proauct70n of the MTBE or TA~E, is used in spherical form as loose filling m a s017d bed as cat~lyst in the reaction of meth~nol and buty~ene, disadv~n~ages like 214~6~ 6 S~B~ ul~ PAGE
h;gher resista~ce to flow, edge flow as well as fhe wear of ~he catalyst are invol~ed.
To a~oid ~hese disadvantages in a process to ca ~ ou~ c~emica~
reactions in a ~eaction-distillation appa~atus ~t has been ~ro~osed to ~cco~odate the ca~alyst consisfing of macro-porous cross-linked gel p4llets of a polys~y~le sulphonic acid Ln closed pouc~es, which ~e constru~ted from and retained by a wi~e netting and are assigned to a solid ked made to suit ~he ~eac~ion apparatus ~y coilin~ in t~e form of a spiral, c~.
EP-A-O 4~6 954.
It has been further p~u~osed ~or the p~rpose of i p~oving the ma~erial ~ch~n~e ~ro~e~ ~ies of the solid bed catalyst p~r,~;~g ~o cons~ruct t~e catalyst in the shape of e~ n~e bodies like R~schig rings, fo~ which purpose a mixture of cross-l;nk~A
~ty~,e divinyl ben2ene eop~lymer in y~o~l~ form is coex~ruded with the thermoplastic poly~ro~ylene to such an PYch~nge s~ape and is s41phonated a~terwards, cf. FR-A-2 297 083.
~0 This co~pt has been fu~ther developed inasmuch the formed bodies were ~Lodu~ed direc~ly from macro-porous ion ~oh~n~e resins without the ~se of a the~moplastic ~aterial, ~f. DE-A-3 930 515. ~he formed bodies ob~ine~ by this me~hod ha~e ~he expected g~od ~aterial ~Yc~ge prope~ties as well as a good catalytic activity. It is, howe~er, not easy to-~anufacbure these in pro~t;~n quantities and t~ey leave a lo~ to be desired ~ega~ding ~heir nech~n;cal ~LLengLh.
33 From US 4 ~50 052 supported ~a~alyst~ are known 7n ~he form of a pac~ing, whic~ can be coated with a poly~er made of vin~l aromati~ mononers and can be su~seguently sulphonated. For this ~ul~se the poly~er is dissolved, applied to the s~pport an~
~he solvent is ~hen ~emoved again. A ~is2d~antage of this process and/or of the catalyst prP~09~ in ~his ~anner is that the polymers men~ioned cannot be stron~ly c~oss-lin~e~ as otherwise they could no~ be ~iscQl~e~. The result o~ ~his is that ~hey can be corroded, separated or dissolved by the 21~5fi~i~
S~BSl~ U'l'~` 3?AGE
reacticn ~ixture also. ~n addition, in the r~nne~ ~entioned, no macro-po~osity for t~e poly~er can be achieved.
The ob~ec~ of the in~en~on is to produce a ~ uL~ed catalyst $ with ~ater7al ~Y~-hRnge p~operties which can be also ~Lo~ ce~ in prod~ion qu2ntities.
Th~s ob~ective is ac~ieved by suppo-ted catalysts accord;ng to the cl~im~ 1 to 14 as well ~s ~y a process to carry ou~
c~emical reactions by using these supported ~atalysts according to claLms 15 to 24.
The ~u~o~ed c~talysts according to t~e invention in t~e form of p~ckin~ are cohstructed from a basic body ~o~C~ting of open poro~s ~u~o~L ma~erial, on the external and intern~l sur~ace of which a macro-porous ion e~-h~n~e resin is affixed me~han~cally and/or chemically.
A che~ical affixing ma~ be preferred and is obt~ined, ~or example ~y sil~ ing the surface o~ the open-po~ous ~u~o~
~atexial with su~sequent polymerisation ~uild-up.
The packing of the supporte~ ~atalyst is constructed as R~ ;g rings, Berl s~adles, ~orus saddles, packing rings W7t~ web o~
cross web, Pall rings, o~her hollow bod~es, hollow sphe~es, ordered packages, ho~eycom~ bodies and the like~with a proportion o~ the hollow space o~ ~he ma~ro ~OL~uS ~on e~ n~e resin ~eLng 5 to g5 ~.
The SUp~vr L material o~ the aforementioned ~p~uLLed ~atalys~
consists of open-pore glass, sinte~ed gl~ss, open-pore ceramic material on al~minium silioate ~ase, sintered glass ceramics, foam ~eramics, ac~iva ed c~rh~n or activa~ed coke.
In the case of sintered glass o~ sintered glass cerami~s ~he surface area can be increased by a prio~ treatme~t with aqueous alk~i hyd~uxide solution. By this the nllmh~r of silanol groups on the surface will ke incre~sed o~ the one hand, wh~h surface 21~366~
i S~B~ ul~ PAGE
is ~hen accessi~le for ~ n;s~tion and by ~he etching process a rougher surface is cre~ed on the othe~, thereby favouring a me~h~n;cal af f i~; ng on the polymer applied.
While glass with open pores, sintered glass, sintered glass ics or cera~ic ~terial with open pores are c~mr~rcial~y a~ e al~eady ~n a basic or p~ckin~ form suit241e for material e~ch~nge ~uuposes, activ~ed c~r~on or ac~ivated coke . with suitable pore sizes can be use~ according to the in~en~ion 1~ for cat~lyst beds. Suitable po~e sizes are obtained f~om bulk material a~ter a selection process ~rom sui~able sieved - material in selected size ranges~
T~e macro-poro~s ion ~Y~ nge resin on and in the ~u~o~
~aterial is preferably a macro-porous cross-linked poly~yre~.e sulp~onic acid, where~y a diferen~ degree o~ cro~s-l;nk;ng can be accomplished to correspond wit~ the requLrements by using greater or lesser a~ounts of di~nyl be~zene or diisopropenyl benzene. ~he polymer is preferably cross-linked to such a high degree, ~hat it cannot be disso~ed by ~he rea~tion mixture of the reaction to be c~taly~ed.
The ion ~Y~h~nge ~esin can be appl~ed to the suppart material by two different proc~s~.
~n case of ~he so called i~prey~.ating polyme~isIng ~ ess the for~ed ho~7es are i~ yrlated with the rea~tion mixture, the ~ s~ imp~egna~ing solution is removed ~nd subsequently ~he poly~erisation is carried out.
In ~ase of ~he precipitating poly~erising proce~s the pa~ing is in ~ in the reaction mixture during the polyme~isation.
The ad~antages of the pre~ipitation polymerising process are a very uniform dis~ribution o~ the polymer Ln the pores of the support ~aterial, in ~ddi~70n a high porosity, since the sol~ent can act ~s a pore former, as ~ell as the sLmple pxoduction man~er, since no steps are required to even out ~he distribution of ~he mono~ers on the support.
214~6~
~BS~ ul~ PAGE
An addi~ion~l ad~antage is that the polymRr content in the comple~ed ion e~h~ resin can be set simply by ~he ratio of a suitable solven~ to ~he nono~er mixture and that ~he polymer, when using the appLu~.ia~e solven~, is already in the swollen form so that po~ dam2ge of the ~ L ma~erial by the sw~ g process can be avoided to ~ great exten~. Ne~h~nol or ~-oct~ne, as ~ell as pent~de~Ane may ~e used as solvents. A
C~- to ~l7-n-paraf~in fraction can also be used.
i~ By the pro~ess ~entioned ~ ma~r O POL~US poly~er is pro~r~e~ in t~e pores and on the surface of porous p~cking, which will su~sequen~ly receive ion ~c~nge properties by su~phonation.
In case of the precipi~ating polymerisation process the poly~erisation is carried out depending on the ~o~n~aLion of ~he original materials sLy~.e and divinyl benzene or disopropyl benzene in the pore former or o~ ~he sol~ent in the pores of the packing up to ~hat degree of polymerisation, ~t which the formed poly~er in fla~y form beco~ insoluble in the pore for~er and/or the solvent and precipitates. The polymer fl~kes produced in this manner in ~e pores of the ~up~uLL
m~ter~al can be affixed in the pores of the suppo~t material purely ~h~n;C~lly and zre pro~ected from mechanical damages by the surrolm~in~ ~u~o~ mat~ri~l.
For cert~in rea¢tions it is useful to ~reat supported catalysts of ~he type described abo~e with G~oup7 or Group 8 metals of the periodic ta~le, particula~ly with p~ ium, platinum, ruthenium or rhodium ~n q~antities of 0.1 ~o 100 g/~g of ~he ion e~ nge res~n.
As has alrea~y ~een ;nfli~ted, ~he polymer can be addit~onally a~fixed che~ically on the $Upport material. A suitab~e ~hemical coupler is used ~o~ this purpose. ~or example sil2nes are sui~a~le co~plers for all formed hodies whi~h have OH gL~uys on their sur~a~es.
- 214~6~
I S~B~ Ul~ PAGE
If ~he polymer to be coupled has a Yinyl~c monomer base, ~inyl-group ~ ~ ing s;l~nes are prefer~ed as couplers, par~;Y
phenyl-7Jinyl diethoxysilane, phenyl-methyl vinyl silane, ~riethoxy-~inyl ~ nP or trichlor-~inyl silane.
~he supporte~ catalyst can be pro~eA by impregnating the pa~king with 0.1 to ~0% by weight with a mixture cnn~is~ing of 10 to 80, preferab7.y 30 to 70% by weight o~ S~yl~-e, ~ to 25, preferably 5 to 10~ by ~eight of di~inyl h~n~sne~ 1 to 8~, prefera~ly 20 to S0~ ~y weight of a pore forme~ or of a sol~en~
as wel~ as an effective quantity of a polymerisation in7tiator.
carryi~g out the polymerisation reaction under a te~peratuXe _ncre2se of 30- to 90~; and subsequently tre2ting ~he polymer material affixed in the pores of the pack~ng with a sulphonating 2cid. In this case the proportion ~y weight of t~e pore former or of ~he solvent is selected so that the proportion by weight of the ~ixture of ~y~-ene and di~inyl benzene adds up to 100~ by weigh~.
A supported ~talys~ pro~tlce~ according ~o ~he precipi~ating polymerisation process can be obt~;n~ by adding a mixture of 10 to 80, pre~erably 20 t~ 50% by ~eight o~ s~yrene, 2 to 2~, p~eferably ~ to 10~ ~y weight of di~i~yl behzene, 1 t~ 88, preferably 20 to 50% ~y weig~ of a pore former or solvent as well ~s 2n ef~ective quantity of a polyme~isati~n ini~iator on the one hand and a ~- to ~l7-n-par~ffin fraction on the other in a weight ra~io of 10 to 1 to 1 to 10, to 5 to 50~ by wei~h~
of the suppo~t material, b~sed on the total mixture~
~onditioning it under ~acuum, polymerising, was~ m g out the e~c~ pore former and ex~ern~lly adheri~g polymex gel, followed by sulphona~ing.
As po~e for~ers ~6- to ~ alkanes, e.g. n-~eptane, pentadecane, i-octane ~s well as Cg~ to C~-fractions of the n-paraffin production ~n ~e used. These pore forme~s ha~e good solubility for the ~y~e and divinyl ~enzene ~onomers used for the produ~ion of t~e ion exchange ~esin, but only 2 sligh~
- 2i4~66~
S~B~ ul~ ~A~E
sw~llin~ ability for the polymer produced tcf. Catalytic ~hemistry, Bruce C~ Gates, John Wiley & Sons, lg92, p.221).
In th~s manner a solid phase, con~isting pre~erably Of 5 m~L.,.~.h~es, is formed in ~e hollow spaces of ~e ~u~o~ and on the support material, and the volume ori~inal~y o~ r;ed by the sol~ent for t~e mono~ers remalns as ~acro-pores after the remo~al of ~he solvent, which pass th~ough the entire cross-linked polysty~ene and thus enable a good ~ of the reacting ~aterials fo~ the intpn~ chemical reactions after sulp~ona~ion. At the same ti~ne arl increase of ~he active sur~ac:e can ~e achieved by this.
Thi~ is why in a pre~e~red ~ho~;~ent the pore ~ormers can ke also solvents for the m~nomer mixture in case o~ the pre~ipitation polymerisation. ~n case of the precipitation polymerisation lower ~lkAnol$ like methanol are also suita~le as sol~ent. Combina~ions of solYent and pore former can also be used~
~0 The sulphonating a~id may be an ~ro~ati~ or an ~ h~t~c sulp~ir, acid, chlorosnlrhn~ic acid or s~lph~ric acid.
Furthe~ e, sl~ ur dioxide as well as sulphur dioxide addi~ion c~o~ ds like tha~ of dioxane, dime~hyl ~ l;ne or ~5 pyri~iine are suiWle.
S~lrht$ric acid is less prefera~le, as t~e ~ ,~dtion n~c~s~ry for ~deglla~e sulphonation has a notice~hl~ o~ C;rl~
a~fe~ ~nd may lead ~o ~he disinteyLa~ion of the polymer fra~e.
.
Prefer~ed aro~a~ic sulphonic acids are ~enzene sulphonic acids an~ p~efer~ed ~liEJhatic sulph~ acids ~e me~yl sulphonic ~c~ids ~
35 In a fu~ther preferred e~odiment ~he aci~s ~na~ also con~ain sol~ents like ch3 oro~o~, ni~rome~hane or ac:etonitrile~
2 1 ~
SUB~ U~. PAGE
~he ~or~ed ca~lysts accord~ng to the in~ent70n are generally use~ to car~y out ~he chemi~al reactions o~
et~erification, esteri~ication, ~y~ogenation~ a~kylisation, hydration, dimerisation, oligomerisation or com~nation of these as well as the ~ e~ive ~e~e reactions.
Part;~T1~r1Y preferred is the ca~rying out o~ one of the a~ove ~entio~e~ che~ic~l reactions with simultaneously applied separating cpera~ion ~ike adsorption, abso~ption, extraction, stripping, distillation, rectification, fraction~ting, m~Lb.~le process or the like to separa~e the required products. In this case the countaL ~ L of the gaseous or ~iguid phase is suitable for a single or multiple phase gaseous and liquid reac ion, since the ~u~o~ed catalysts a~cording to the invention have a ~igh deg~ee of spacing and thus ca~se a low pressure loss.
A ~referred chemical reac~ion for using the su~ Led ~talys~
acc~rding to t~e invention is the chemical ~eac~ion of e~herification and ~he ~ep~ration o~ the reaction products by reactive distillation to ob~ain ~ertiary a~kyl e~hers from the reaction of ~lk~noles with alkenes; such as to o~taLn X~BE ~ro~
the re~ction of mRthanol ~ith i-butylene: to o~tain i-propyl- -tertiary ~u~yle~her (PTB~) fron the ~eaction o~ i-propanol with i-b~tylene; to o~Ain ETB~ f~om the reactlon of i-~utylene with ethanol; or to obt~tn TA~E from the reaction of-i-pentene-tl~
o~ i-pentene-(Z) wi~h me~hanol. Fu~ther preferred reactiRns are the produc~ion of i-propanol $~om the reaction of propylene w~th water and the ~L~du~Lion of ~erti2ry butyl al~ohol tTBA) ~y reacting i-bu~ylene w~th wate~.
This present inventlon is exp~ained in detai~ ~sed on ~he $ollowing exa~ples as well as the results con~ine~ in Ta~les 1 ~nd 2 and t~e ~igs.1 and ~.
SUBSlllu l~; PAGE 21 4 ~i 6 fi ~1 Exunple 1 AS `;~G~I.. material formed bodies made of open-porous sintered glass in t~e ~orm of ~ ;g riI~gs wit~ the rl;me~ClQn~ 8.8 mm:
g mm (ou~side diamete~ x heig~t).
Th~s suppor~ material is characterised ~y a su~face of up to 0.4m2/g and a pore volume of up to 70%. ~e po~e diame~er can be ~aried ~om 1.~ ~m to 400 ~m, the ~ ~ra~Le resistance is up to ~O~
40 ri eC~c of the afore~entioned r~ngs have a ~aCs of 12.~ g and were i~ eyllated wi~h a mix~ure of 22.7 g styrene, 13.7 g pen~ c~ne, 2.9 g di~inyl ~enzene ana 50 mg azo-isobuty~onitrile. The ~cyl,a~ion solution no~ accom~oda~ed in the pores was remo~ed. The impregnated rings were rl~e~ in~o a sealed, p~essuri~ed metal con~nPr and were polyme~ised a~ a ~empe~a~u~e of app~ox. 7SC in a heating c~hinet for ~he period of 10 h. The ~Les~ul~ised contai~er is npc~ssary to ~L~vel~L the changing o~ the ~onomer mixture during the poiymerisa~ion by ~apo~isation p~c~ s. ~he polymer content of ~e rings treated in ~his ~anner was approx. 20 to 25~ by weigh~. T~e rings were cooled af~erwards ~o r~om temperature and su~jec~ed to sulphonation. ~OO ~L of the formed bodies obt~ine~ were co~ered ~omple~ely with chloroform and ~ade to react wi~h ~0 m~
of chloros~lrh~7~ acid ~or 20 h while excl~ding ~o~sture.
Subse~uen~ly the reaction solu~ion was pou~ed slowly on ice, the formed bod~es were rinsed wit~ chlorofor~ and rinsed ~ith me~hanol and deiQ~ 7 C~d water to comple~ely remove the sulphona~ing agent and acid. The formed bodies were s~o~ed in water.
Example 2 lZ.5 g cf ~he support m~terial described in ~xam~le 1 ~ added ~o a mixture with ~he weight ra~o of 1 to 1 o~ 22.7 g ~y~ne, 2.9 g divinyl benzene, 1~.g g i-oc~ane, ~.05 g azo-isobu~yLo~ rile on the one hand and C~- to ~ n-pa~aff~n fraction on the other, so that the formed bodies to be i~pregnated were fully cove~ed. A~erw~rds ~he mix~ure was S~ ul~ PAG~ 21~5~
conditioned for 2 ~in under Yacuum to fill ~11 the pores T~e mixtu:re was subse~auently hea~ed for 16 h at 60-~.
T~e ~ er gel ~u~r~o~ ;n~ the f~r~ed bodies as well as the pore for~er were washed out after the co~pletion ~f t~e reac~ion ~i~h chloroform. The formed bodies produced thus cont~;~e~ approx. lU ~6 by weight po~y~er.
By repeating the t~eatment according to this ~ethod tlle pc~lymer ~0 content c~ e incre~sed to G~rox. 20 ~ by weigh~
~00 mL of the formed ho~ies obtained were fully ~vc~ed with chloroform and ma~e to reac} with 50 mL chlorosulphonic acid for 20 h while excluding moisture. Subsequently the reaction solution w~s you~ed slowly on ice, the formed bodies were ~insed with ~hloroform and ri ~ed wi~h methanol and deionised wa~er to comp~etely ~ v~ the sulphonating agen~ an~ acid. The fo~ed bodies were s~ored in wate~.
The ab~l~v-~tions used in Table 1 have the ~ollowing me~n;n~s:
Cap: Capacity of ~e catalys~ used n~: Mole flow of the co~o~n~ i T: Dwell time ~o~-ve7sion of the componen~ i Ys Yield of M~BE based on the comro~ent i ¢~rnn~t i: NeOE or I~
~eOH: Neth~ol IB~ u~lene sSDCmT: Sulphona~ed ~L~r~"eJdi~inyl-~enzene ~opolymer, macro-poro~s, produced by i~p~y~.a~ing polymeris~tion sSD~m~: Su~p~onated sty~ene~ivinyl-~enzene ~opo~ymer, macro-po~ous, produced by precipl~ting polymerisation sSD~: Sulphona~ed ~L~Lel,e/divin~l copolymer MPI: ~acro-porous ion e~h~n~e rings S~B~lllul~ PAGE 214 5 ~ ~
~a~le 2 sho~ ~he effe~tive reac~ion speeds of ~he ~TBE
form~tion. They are based on the c~p~C-ity of ~he catalyst on the one hand, on the mass on the other, and finally on the bulk volume of the dxy catalyst.
~he bulk density of the dry catalyst was est~h~i~he~ by weighing t~e mass ~hlch takes up a given bul~ ~olume, or by measuring the volume o~ a ~i~en mass. In the present case a volume has been assu~ed.
Table 1~ ~enta~ settin~s of the ca~alysts used The ~L~uLe ana ~emperature ha~e been held oonstant in all experiments tp = 20 x 10S P~; ~ = 65~C) ~xperi~en~ Cata}ys~ Cap. ~eigh~ n~ n~
~ 1 sSDCmT 0.506 1886 30 28.57 ¦ 2 sSD~ 0.419 1804 30 28.57
SUB~ U~. PAGE
~he ~or~ed ca~lysts accord~ng to the in~ent70n are generally use~ to car~y out ~he chemi~al reactions o~
et~erification, esteri~ication, ~y~ogenation~ a~kylisation, hydration, dimerisation, oligomerisation or com~nation of these as well as the ~ e~ive ~e~e reactions.
Part;~T1~r1Y preferred is the ca~rying out o~ one of the a~ove ~entio~e~ che~ic~l reactions with simultaneously applied separating cpera~ion ~ike adsorption, abso~ption, extraction, stripping, distillation, rectification, fraction~ting, m~Lb.~le process or the like to separa~e the required products. In this case the countaL ~ L of the gaseous or ~iguid phase is suitable for a single or multiple phase gaseous and liquid reac ion, since the ~u~o~ed catalysts a~cording to the invention have a ~igh deg~ee of spacing and thus ca~se a low pressure loss.
A ~referred chemical reac~ion for using the su~ Led ~talys~
acc~rding to t~e invention is the chemical ~eac~ion of e~herification and ~he ~ep~ration o~ the reaction products by reactive distillation to ob~ain ~ertiary a~kyl e~hers from the reaction of ~lk~noles with alkenes; such as to o~taLn X~BE ~ro~
the re~ction of mRthanol ~ith i-butylene: to o~tain i-propyl- -tertiary ~u~yle~her (PTB~) fron the ~eaction o~ i-propanol with i-b~tylene; to o~Ain ETB~ f~om the reactlon of i-~utylene with ethanol; or to obt~tn TA~E from the reaction of-i-pentene-tl~
o~ i-pentene-(Z) wi~h me~hanol. Fu~ther preferred reactiRns are the produc~ion of i-propanol $~om the reaction of propylene w~th water and the ~L~du~Lion of ~erti2ry butyl al~ohol tTBA) ~y reacting i-bu~ylene w~th wate~.
This present inventlon is exp~ained in detai~ ~sed on ~he $ollowing exa~ples as well as the results con~ine~ in Ta~les 1 ~nd 2 and t~e ~igs.1 and ~.
SUBSlllu l~; PAGE 21 4 ~i 6 fi ~1 Exunple 1 AS `;~G~I.. material formed bodies made of open-porous sintered glass in t~e ~orm of ~ ;g riI~gs wit~ the rl;me~ClQn~ 8.8 mm:
g mm (ou~side diamete~ x heig~t).
Th~s suppor~ material is characterised ~y a su~face of up to 0.4m2/g and a pore volume of up to 70%. ~e po~e diame~er can be ~aried ~om 1.~ ~m to 400 ~m, the ~ ~ra~Le resistance is up to ~O~
40 ri eC~c of the afore~entioned r~ngs have a ~aCs of 12.~ g and were i~ eyllated wi~h a mix~ure of 22.7 g styrene, 13.7 g pen~ c~ne, 2.9 g di~inyl ~enzene ana 50 mg azo-isobuty~onitrile. The ~cyl,a~ion solution no~ accom~oda~ed in the pores was remo~ed. The impregnated rings were rl~e~ in~o a sealed, p~essuri~ed metal con~nPr and were polyme~ised a~ a ~empe~a~u~e of app~ox. 7SC in a heating c~hinet for ~he period of 10 h. The ~Les~ul~ised contai~er is npc~ssary to ~L~vel~L the changing o~ the ~onomer mixture during the poiymerisa~ion by ~apo~isation p~c~ s. ~he polymer content of ~e rings treated in ~his ~anner was approx. 20 to 25~ by weigh~. T~e rings were cooled af~erwards ~o r~om temperature and su~jec~ed to sulphonation. ~OO ~L of the formed bodies obt~ine~ were co~ered ~omple~ely with chloroform and ~ade to react wi~h ~0 m~
of chloros~lrh~7~ acid ~or 20 h while excl~ding ~o~sture.
Subse~uen~ly the reaction solu~ion was pou~ed slowly on ice, the formed bod~es were rinsed wit~ chlorofor~ and rinsed ~ith me~hanol and deiQ~ 7 C~d water to comple~ely remove the sulphona~ing agent and acid. The formed bodies were s~o~ed in water.
Example 2 lZ.5 g cf ~he support m~terial described in ~xam~le 1 ~ added ~o a mixture with ~he weight ra~o of 1 to 1 o~ 22.7 g ~y~ne, 2.9 g divinyl benzene, 1~.g g i-oc~ane, ~.05 g azo-isobu~yLo~ rile on the one hand and C~- to ~ n-pa~aff~n fraction on the other, so that the formed bodies to be i~pregnated were fully cove~ed. A~erw~rds ~he mix~ure was S~ ul~ PAG~ 21~5~
conditioned for 2 ~in under Yacuum to fill ~11 the pores T~e mixtu:re was subse~auently hea~ed for 16 h at 60-~.
T~e ~ er gel ~u~r~o~ ;n~ the f~r~ed bodies as well as the pore for~er were washed out after the co~pletion ~f t~e reac~ion ~i~h chloroform. The formed bodies produced thus cont~;~e~ approx. lU ~6 by weight po~y~er.
By repeating the t~eatment according to this ~ethod tlle pc~lymer ~0 content c~ e incre~sed to G~rox. 20 ~ by weigh~
~00 mL of the formed ho~ies obtained were fully ~vc~ed with chloroform and ma~e to reac} with 50 mL chlorosulphonic acid for 20 h while excluding moisture. Subsequently the reaction solution w~s you~ed slowly on ice, the formed bodies were ~insed with ~hloroform and ri ~ed wi~h methanol and deionised wa~er to comp~etely ~ v~ the sulphonating agen~ an~ acid. The fo~ed bodies were s~ored in wate~.
The ab~l~v-~tions used in Table 1 have the ~ollowing me~n;n~s:
Cap: Capacity of ~e catalys~ used n~: Mole flow of the co~o~n~ i T: Dwell time ~o~-ve7sion of the componen~ i Ys Yield of M~BE based on the comro~ent i ¢~rnn~t i: NeOE or I~
~eOH: Neth~ol IB~ u~lene sSDCmT: Sulphona~ed ~L~r~"eJdi~inyl-~enzene ~opolymer, macro-poro~s, produced by i~p~y~.a~ing polymeris~tion sSD~m~: Su~p~onated sty~ene~ivinyl-~enzene ~opo~ymer, macro-po~ous, produced by precipl~ting polymerisation sSD~: Sulphona~ed ~L~Lel,e/divin~l copolymer MPI: ~acro-porous ion e~h~n~e rings S~B~lllul~ PAGE 214 5 ~ ~
~a~le 2 sho~ ~he effe~tive reac~ion speeds of ~he ~TBE
form~tion. They are based on the c~p~C-ity of ~he catalyst on the one hand, on the mass on the other, and finally on the bulk volume of the dxy catalyst.
~he bulk density of the dry catalyst was est~h~i~he~ by weighing t~e mass ~hlch takes up a given bul~ ~olume, or by measuring the volume o~ a ~i~en mass. In the present case a volume has been assu~ed.
Table 1~ ~enta~ settin~s of the ca~alysts used The ~L~uLe ana ~emperature ha~e been held oonstant in all experiments tp = 20 x 10S P~; ~ = 65~C) ~xperi~en~ Cata}ys~ Cap. ~eigh~ n~ n~
~ 1 sSDCmT 0.506 1886 30 28.57 ¦ 2 sSD~ 0.419 1804 30 28.57
3 MPI 4.63 1500 30 2$.57
4 A15 ~.75 1~28 30 Z8.57 SPC118 4.40 lg32 30 28.57 6 sSDCmF 0.S~5 2011 30 28.~7 ;~ent Catalyst ~(min~ C~llve~ion t%) Yie1d Y ~%) 1 sSDCmT 25.1g 2.7 2.8 2.7 ~.8 2 sSD~ 25.18 0.33 0.35 0.33 0.35 3 MPI 25.18 1.85 l.9S 1.86 1.96 4 A15 25.18 7.00 7.3 7.0 7.3 SP~118 25.18 7.5 7.g 7.~ 7.9 ~ ~SDrmF 2~.18 0.~4 0.~7 ~.51 0~57 ~able 2: Results of ~he catalysts used Experiment Cat. p Rate e~Ra~e ~ ~ate V~
[gl~l ~ S eg)l [nol/rs g~O3 [D~y~ lP
sSD~T 0.3~8 14.1 7.13 2.34 2 sSDC 0.328 2~240.94 0.31 3 ~I 0~3~4 1.3~6.20 2.38 4 ~1~ 0.577 3.g218.14 10.46 SP~118 0.506 4.4319.49 9.86 ~ sSDCmF 0.3~8 2.271.3~ 0~44 Rate Z,~,,, ~rBE: Reaction speed of the ~BE for~ation - if Z -- e: Based on ~e eguiv~lent of the resin used - i~ Z = ~: B~sed on the ~ss of ~he res~ used - if ~ - V: Based on t~e b~ rolume of the resin used SUB~ ul~: PAGE 21 45~
The ~a~alyst of E~periment 1 ~as p~ 7~e~ according to Example 1.
me c~a~alyst of Experiment 2 was p~o~lllçe~ in an a~alogous
[gl~l ~ S eg)l [nol/rs g~O3 [D~y~ lP
sSD~T 0.3~8 14.1 7.13 2.34 2 sSDC 0.328 2~240.94 0.31 3 ~I 0~3~4 1.3~6.20 2.38 4 ~1~ 0.577 3.g218.14 10.46 SP~118 0.506 4.4319.49 9.86 ~ sSDCmF 0.3~8 2.271.3~ 0~44 Rate Z,~,,, ~rBE: Reaction speed of the ~BE for~ation - if Z -- e: Based on ~e eguiv~lent of the resin used - i~ Z = ~: B~sed on the ~ss of ~he res~ used - if ~ - V: Based on t~e b~ rolume of the resin used SUB~ ul~: PAGE 21 45~
The ~a~alyst of E~periment 1 ~as p~ 7~e~ according to Example 1.
me c~a~alyst of Experiment 2 was p~o~lllçe~ in an a~alogous
5 manr~er, but withou~ pore former~ and tbus is not macro-porous.
~his cat~lyst is obviously po~ in the tes~ o~t on of the ~TBE for~nation than that of Ex~ri~ent 1.
~e ca~alyst of e3~periment 6 ~s pro~uce~ ac:~or~ing to ~rople 2. All:hough as far as a~ti~ity is cnnc~ned it is situated be70w tha~ o~ the catalyst of Experiment 1, its pradu~tion, howeYe~, ~s less castly. Experi~ents 3 to 5 ~re comparison exper ~ nts with s~?h~r.d ion eY~h~n~ers. A15 is an amberlite of ~he co~r~ny Rohm & ~aas and SPC118 a product of ~he Bayer c4~r~ny. The polymer rings wi~h the designa~ion o~ MPI are described in EP O 417 4~7 A1.
The ~ollowing Figs.l a~d 2 of the drawing show the mac~o- and meso-pore distribution of t~e catalyst accordi~g to Ex~e Lment 1.
The ab~r~iations stand ~or:
in Fig.l:
V~ ~ Volu~e o~ the ma~ e-~ in mL/g measured by me~uly po~osimetry V~K~O = Volu~e of the adsor~ed helium in t~e macropo~es in mL/g (N~T.P~) measured ~y hel~um adso~p~ion S~0 = Surface of the ~a~ ~o~ n mZ/g r~ = A~er~ge pore radius (in ~his case ~hat of the macropore) ! in Fig.~:
S~ = Spe~ific surface of the spec~en in m~/g measured according ~o ~e BET me~hod5 S~ = S~rface ~asea on the st~n~rd iso~herms according to ~ec~oux S~0 = S~rfa~e of ~he mesopores ~n m2~g V~ = Volume of the mesopo~es u 1 ~; PAGE 21 A 5 6 ~ ~
According to mPA~ 72~ the diame~ers are for:
mic~ro~?ores c ~
~esopo~es 2 nm tc~ 50 nm mi~ OL ~;:i ~ 50 ~m .
~his cat~lyst is obviously po~ in the tes~ o~t on of the ~TBE for~nation than that of Ex~ri~ent 1.
~e ca~alyst of e3~periment 6 ~s pro~uce~ ac:~or~ing to ~rople 2. All:hough as far as a~ti~ity is cnnc~ned it is situated be70w tha~ o~ the catalyst of Experiment 1, its pradu~tion, howeYe~, ~s less castly. Experi~ents 3 to 5 ~re comparison exper ~ nts with s~?h~r.d ion eY~h~n~ers. A15 is an amberlite of ~he co~r~ny Rohm & ~aas and SPC118 a product of ~he Bayer c4~r~ny. The polymer rings wi~h the designa~ion o~ MPI are described in EP O 417 4~7 A1.
The ~ollowing Figs.l a~d 2 of the drawing show the mac~o- and meso-pore distribution of t~e catalyst accordi~g to Ex~e Lment 1.
The ab~r~iations stand ~or:
in Fig.l:
V~ ~ Volu~e o~ the ma~ e-~ in mL/g measured by me~uly po~osimetry V~K~O = Volu~e of the adsor~ed helium in t~e macropo~es in mL/g (N~T.P~) measured ~y hel~um adso~p~ion S~0 = Surface of the ~a~ ~o~ n mZ/g r~ = A~er~ge pore radius (in ~his case ~hat of the macropore) ! in Fig.~:
S~ = Spe~ific surface of the spec~en in m~/g measured according ~o ~e BET me~hod5 S~ = S~rface ~asea on the st~n~rd iso~herms according to ~ec~oux S~0 = S~rfa~e of ~he mesopores ~n m2~g V~ = Volume of the mesopo~es u 1 ~; PAGE 21 A 5 6 ~ ~
According to mPA~ 72~ the diame~ers are for:
mic~ro~?ores c ~
~esopo~es 2 nm tc~ 50 nm mi~ OL ~;:i ~ 50 ~m .
Claims (24)
1. Supported catalyst in the shape of packing and constructed from an open porous support material, on whose external and internal surfaces as well as in the pores a macro-porous ion exchange resin is affixed mechanically and/or chemically, which can be produced by impregnating or completely covering the support material constructed as packing with a mixture of polymerisable monomers as well as solvent and/or pore former, carrying out the polymerisation reaction and, if applicable, functionalising to introduce ion exchange active groups.
2. Supported catalyst according to claim 1, characterised in that the packaging is constructed as Raschig rings, Berl saddles, torus saddles, packing rings with web or cross web, Pall rings, other hollow bodies, hollow spheres, ordered packages, honeycomb bodies with a proportion of the hollow space of the macro-porous ion exchange resin being 5 to 95%.
3. Supported catalyst according to claim 1 or 2, characterized in that the support material consists of open-pore glass, sintered glass, open-pore ceramic material on aluminium silicate base, sintered glass ceramics, foam ceramics, activated carbon or activated coke.
4. Supported catalyst according to any one of the claims 1 to 3, characterised in that on its surface open-pore support material carrying OH groups is reached with vinyl group carrying silane as a coupler on which surface acidic ion exchange groups are affixed by subsequent sulphonation.
5. Supported catalyst according to any one of the claims 1 to 4, characterised in that the macro-porous ion exchange resin is a macro-porous cross-linked polystyrene sulphonic acid.
6. Supported catalyst according to any one of claims 1 to 5, treated with group 7 or Group 8 metals of the periodic table, partially with palladium, platinum, ruthenium of rhodium in quantities of 0.1 to 100 g/kg of the ion exchange resin.
7. Support catalyst according to any one of the claims 1 to 6, obtained by impregnating the packing with 0.1 to 60% by weight of a mixture consisting of 10 to 80, preferably 30 to 70% by weight of styrene, 2 to 25, preferably 5 to 10%
by weight of divinyl benzene, 1 to 88, preferably 20 to 50%
by weight of a pore former or of a solvent as well as an effective quantity of a polymerisation initiator; carrying out the polymerisation reaction under a temperature increase of 30° to 90°C; and subsequently sulphonating.
by weight of divinyl benzene, 1 to 88, preferably 20 to 50%
by weight of a pore former or of a solvent as well as an effective quantity of a polymerisation initiator; carrying out the polymerisation reaction under a temperature increase of 30° to 90°C; and subsequently sulphonating.
8. Supported catalyst according to any one of the claims 1 to 7, obtained by adding a mixture of (A) 10 to 80, preferably 20 to 50% by weight of styrene, 2 to 25, preferably 5 to 10% by weight of divinyl benzene, 1 to 88, preferably 20 to 50% by weight of a pore former or solvent as well as an effective quantity of a polymerisation initiator and (B) a C14- to C17-n-paraffin fraction in a weight ratio of (A):(B) of 10:1 to 1:10, to 5 to 50% by weight of the support material, based on the total mixture, conditioning under vacuum, polymerising, washing out the excess pore former and externally adhering polymer gel and subsequently sulphonating.
9. Supported catalyst according to any one of the claims 7 or 8, characterised in that the styrene is replaced partially by fluoro-styrene.
10. Supported catalyst according to any one of the claims 1 to 9, characterised in that the pore former is a C6- to C16-alkane, such as n-heptane, pentadecane, i-octane or a mostly C4- to C13 containing n-paraffin fraction.
11. Supported catalyst according to claims 1 to 10, characterised in that the solvent is methanol, i-octane, pentadecane or a C14- to C17-n-paraffin fraction.
12. Supported catalyst according to any one of the claims 1 to 11, characterised in that the functionalising is carried out by means of a sulphonating acid, preferably an aromatic or aliphatic Sulphonic acid, chlorosulphonic acid or sulphuric acid.
13. Supported catalyst according to claim 12, characterised in that the aromatic sulphonic acid is a benzene sulphonic acid.
14. Supported catalyst according to claim 12, characterised in that the aliphatic sulphonic acid is a methyl sulphonic acid.
15. Process to carry out the chemical reaction of etherification, esterification, hydrogenation, dimerisation, hydration, alkylisation, oligomerisation or combination of these, characterised by using a supported catalyst according to any one of the claims 1 to 14.
16. Application according to claim 15, characterised by simultaneously applied separating operations like adsorption, absorption, extraction, stripping, distillation, rectification, fractionating or membrane process.
17. Application according to claim 15 or 16, characterised by the counter flow of the gaseous and liquid phases.
18. Process according to any one of the claims 15 to 17, characterised by the reaction of alkanols to tertiary alkyl ethers.
19. Process according to any one of the claims 15 to 18, characterised by the reaction of methanol and i-butylene to methyl tertiary butyl ether (MTBE).
20. Process according to any one of the claims 15 to 18, characterised by the reaction of i-propanol and i-butylene to i-propyl tertiary butyl ether (PBTE).
21. Process according to any one of the claims 15 to 18, characterised by the reaction of i-butylene and ethanol to ethyl tertiary butyl ether (ETBE).
22. Process according to any the of the claims 15 to 18, characterised by the reaction of i-pentene-(1) or i-pentene-(2) with methanol to tertiary amyl methyl ether (TAME).
23. Process according to any one of the claims 15 to 17, characterised by the reaction of propene and water to i-propanol.
24. Process according to any one of the claims 15 to 17, characterised by the reaction of i-butylene and water to tertiary butyl alcohol (TBA).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4234779.3 | 1992-10-15 | ||
| DE4234779A DE4234779A1 (en) | 1992-10-15 | 1992-10-15 | Supported catalyst and use of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2145666A1 true CA2145666A1 (en) | 1994-04-28 |
Family
ID=6470537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002145666A Abandoned CA2145666A1 (en) | 1992-10-15 | 1993-10-02 | Support catalyst and use of same |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5780688A (en) |
| EP (1) | EP0664732B1 (en) |
| JP (1) | JP3038012B2 (en) |
| AT (1) | ATE160708T1 (en) |
| AU (1) | AU678400B2 (en) |
| CA (1) | CA2145666A1 (en) |
| DE (2) | DE4234779A1 (en) |
| DK (1) | DK0664732T3 (en) |
| ES (1) | ES2110628T3 (en) |
| FI (1) | FI951698A0 (en) |
| GR (1) | GR3025868T3 (en) |
| WO (1) | WO1994008713A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038395C (en) * | 1994-10-25 | 1998-05-20 | 中国石油化工总公司 | Ion exchange resin catalyzer for synthesising bisphenol and preparation thereof |
| DE19541213A1 (en) * | 1995-11-04 | 1997-05-07 | Rwe Dea Ag | Process for the chemical conversion of substances in a reaction column |
| US6703530B2 (en) | 2002-02-28 | 2004-03-09 | General Electric Company | Chemical reactor system and process |
| AU2004212641B2 (en) | 2003-02-19 | 2009-08-06 | Merck Millipore Ltd. | Composite materials comprising supported porous gels |
| FR2861725B1 (en) * | 2003-11-04 | 2005-12-30 | Arkema | PROCESS FOR THE PURIFICATION OF THE (METH) ACRYLIC ACID OBTAINED BY OXIDATION OF A GASEOUS SUBSTRATE |
| EP1758671B9 (en) | 2004-04-08 | 2014-02-19 | Natrix Separations Inc. | Membrane stacks |
| AU2005251838B2 (en) | 2004-06-07 | 2011-04-21 | Merck Millipore Ltd. | Stable composite material comprising supported porous gels |
| JP4918259B2 (en) * | 2006-01-06 | 2012-04-18 | 株式会社キャタラー | Low molecular organic gas absorbent and fuel vapor processing apparatus using the same |
| EP2051807A1 (en) * | 2006-08-10 | 2009-04-29 | Basf Se | Shaped catalyst bodies with characteristics of ion exchangers |
| DE102007031854B4 (en) | 2007-07-09 | 2017-03-02 | Robert Bosch Gmbh | Process for the production of ceramic bodies with functionalized pore surfaces and subsequently produced bodies |
| KR102178191B1 (en) | 2008-09-02 | 2020-11-13 | 머크 밀리포어 리미티드 | Chromatography membranes, devices containing them, and methods of use thereof |
| EP2208719A1 (en) | 2009-01-15 | 2010-07-21 | Sasol Solvents Germany GmbH | Process for the production of lower alcohols by olefin hydration |
| CA2780095C (en) * | 2009-11-13 | 2018-12-11 | Natrix Separations Inc. | Hydrophobic interaction chromatography membranes, and methods of use thereof |
| JP6272755B2 (en) | 2011-05-17 | 2018-01-31 | ナトリックス セパレイションズ インコーポレーテッド | Layered tubular membrane for chromatography and method of use thereof |
| CN111013173B (en) * | 2019-12-31 | 2021-07-06 | 厦门大学 | Supported catalytic filler and preparation method and application thereof |
| CN113019464B (en) * | 2021-03-11 | 2022-12-13 | 哈尔滨工程大学 | Preparation method of spherical SDB hydrophobic carrier with controllable size and Pt/SDB hydrophobic catalyst |
| CN114989484B (en) * | 2022-07-05 | 2023-03-14 | 厦门大学 | Preparation method of supported catalytic packing for reactive distillation |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2505850B1 (en) * | 1981-05-12 | 1985-06-21 | Rhone Poulenc Spec Chim | PROCESS FOR OBTAINING POLYSILOXANES FROM HIGH MOLECULAR MASSES BY POLYMERIZATION AND REARRANGEMENT OF POLYSILOXANES IN THE PRESENCE OF A CATALYST CONSISTING OF A POROUS MINERAL SUPPORT COATED WITH A POLYMERIC FILM CARRIER OF SULFONIC OR PHOSPHONIC GROUPING |
| US4661411A (en) * | 1986-02-25 | 1987-04-28 | The Dow Chemical Company | Method for depositing a fluorocarbonsulfonic acid polymer on a support from a solution |
| EP0503688A3 (en) * | 1986-02-25 | 1992-09-23 | The Dow Chemical Company | Methods for the preparation of supported fluorocarbonsulfonic acid polymers |
| US4791081A (en) * | 1986-02-25 | 1988-12-13 | The Dow Chemical Company | Supported fluorocarbonsulfonic acid polymers and an improved method for their preparation |
| DE3734138A1 (en) * | 1987-10-09 | 1989-04-20 | Scharmer Klaus Dr Ing | ACID CATALYST AND METHOD FOR PRODUCING THE CATALYST |
| DE3930515A1 (en) * | 1989-09-13 | 1991-03-21 | Veba Oel Ag | FORMKOERPER OF MACROPOROESIS ION EXCHANGER RESINS AND USE OF FORMKOERPER |
| US5244929A (en) * | 1989-09-13 | 1993-09-14 | Veba Oel Aktiengesellschaft | Molded bodies comprised of macroporous ion exchange resins, and use of said bodies |
| CA2054386A1 (en) * | 1990-11-16 | 1992-05-17 | Eric Gustave Lundquist | Acidic catalyst for condensation reactions |
| US5233096A (en) * | 1990-11-16 | 1993-08-03 | Rohm And Haas Company | Acidic catalyst for condensation reactions |
| US5132099A (en) * | 1990-12-27 | 1992-07-21 | Mitsubishi Gas Chemical Company, Inc. | Method for producing hydrogen peroxide |
| US5157162A (en) * | 1991-10-25 | 1992-10-20 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorosulfonic acid-modified clay catalysts |
-
1992
- 1992-10-15 DE DE4234779A patent/DE4234779A1/en not_active Withdrawn
-
1993
- 1993-10-02 JP JP06509572A patent/JP3038012B2/en not_active Expired - Fee Related
- 1993-10-02 AU AU51105/93A patent/AU678400B2/en not_active Ceased
- 1993-10-02 US US08/407,024 patent/US5780688A/en not_active Expired - Fee Related
- 1993-10-02 DE DE59307799T patent/DE59307799D1/en not_active Expired - Fee Related
- 1993-10-02 DK DK93921903.6T patent/DK0664732T3/en active
- 1993-10-02 CA CA002145666A patent/CA2145666A1/en not_active Abandoned
- 1993-10-02 ES ES93921903T patent/ES2110628T3/en not_active Expired - Lifetime
- 1993-10-02 EP EP93921903A patent/EP0664732B1/en not_active Expired - Lifetime
- 1993-10-02 AT AT93921903T patent/ATE160708T1/en not_active IP Right Cessation
- 1993-10-02 WO PCT/EP1993/002696 patent/WO1994008713A1/en active IP Right Grant
-
1995
- 1995-04-10 FI FI951698A patent/FI951698A0/en unknown
-
1998
- 1998-01-12 GR GR980400039T patent/GR3025868T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES2110628T3 (en) | 1998-02-16 |
| AU678400B2 (en) | 1997-05-29 |
| DK0664732T3 (en) | 1998-01-12 |
| FI951698A (en) | 1995-04-10 |
| EP0664732A1 (en) | 1995-08-02 |
| DE59307799D1 (en) | 1998-01-15 |
| JP3038012B2 (en) | 2000-05-08 |
| FI951698A0 (en) | 1995-04-10 |
| JPH07507719A (en) | 1995-08-31 |
| US5780688A (en) | 1998-07-14 |
| DE4234779A1 (en) | 1994-04-21 |
| ATE160708T1 (en) | 1997-12-15 |
| AU5110593A (en) | 1994-05-09 |
| EP0664732B1 (en) | 1997-12-03 |
| WO1994008713A1 (en) | 1994-04-28 |
| GR3025868T3 (en) | 1998-04-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |